JP2022527077A - Inflatable coating composition - Google Patents

Abstract

The present invention relates to an expansive coating composition, a method for coating a substrate with the composition, a substrate coated with the composition, an article comprising the substrate, and an article comprising a battery and / or a battery. In particular, a method for providing fire protection to a vehicle equipped with a lithium ion battery is disclosed. INDUSTRIAL APPLICABILITY The present invention further relates to a method for coating a substrate, which comprises applying the expansive coating composition according to the invention to a substrate at least partially and, if necessary, curing the applied coating composition. Regarding.

Description

The present invention relates to an expansive coating composition, a method for coating a substrate with the composition, a substrate coated with the composition, an article comprising the substrate, and an article comprising a battery and / or a battery. In particular, it relates to a method for providing fire protection to a vehicle equipped with a lithium ion battery.

Commercially available expandable coating compositions generally contain a fairly high amount of TiO ₂ as an important component for obtaining the desired fire protection and mechanical properties of the cured coating, especially charcoal strength, resulting in a result. The cured coatings that are applied are generally white or off-white and cannot be easily dyed. So far, this has not been considered a drawback, as these expansive compositions were generally used for fire protection in construction applications.

Batteries have long been used as a mobile power source. In particular, the development of lithium-ion batteries has increased the power density. As a result, the use of lithium-ion batteries has become widespread in a variety of applications, including home appliances, especially mobile phones, tablets and laptop computers, medical devices, industrial equipment, and especially hybrid / electric vehicles.

However, many batteries, and especially lithium-ion batteries, are vulnerable to thermal runaway, and heat and gas are rapidly expelled from the batteries during thermal runaway, creating a fire risk. Batteries, especially lithium ion batteries, may include electrolyte compositions containing flammable organic solvents that increase the risk of fire associated with batteries, especially lithium ion batteries. Further, the batteries used in the above exemplary applications are primarily battery packs comprising a plurality of individual battery cells. Lithium-ion batteries for hybrid or electric vehicles such as cars, buses, and trucks may contain thousands of individual battery cells. Thermal runaway can be caused by manufacturing defects, heat buildup, internal short circuits, or external impact or trauma. Thermal runaway of one battery cell can affect adjacent battery cells, resulting in an uncontrollable chain reaction, which can result in the entire battery pack igniting, and this fire can ignite these batteries. In the case of a vehicle equipped with, it may spread throughout the vehicle and endanger the driver and passengers.

From the recent incident of a cell phone or electric vehicle igniting due to a thermal runaway of a battery pack, batteries, battery cells, and devices equipped with the batteries, such as mobile phones, tablets, or laptop computers, and hybrid or electric vehicles, and It is clear that there is a need to provide better fire protection for these user devices. Therefore, the expandable coating composition may be useful to provide fire protection for batteries, and in particular articles comprising batteries that are lithium ion batteries.

In addition to providing fire protection as compared to the inflatable coating compositions previously used in construction applications, additional requirements may be important for inflatable coating compositions useful in battery applications. These coating compositions are intended to be used to provide fire protection for consumer products such as cell phones, tablets or laptop computers, or automobiles, so the color of the coating is limited to white or off-white. The expandable coating composition can be dyed to provide a wide range of attractive colors, especially black, without compromising the fire protection and mechanical properties of the cured expandable coating, that is, the desired luster. It is desired in the industry to be able to be formulated to provide a particularly high gloss coating.

Moreover, since the above-mentioned articles protected from battery fire are mobile articles, they can be subjected to mechanical shock or impact. Therefore, there is an industry desire for expansive coating compositions that exhibit improved impact resistance of cured coatings.

In addition, the article described above or the battery case for the article can be made of aluminum or can comprise an aluminum component, so that the expandable coating composition is applied onto an aluminum substrate. Is intended. Therefore, there is further industry hope for expansive coating compositions that exhibit improved adhesion of cured coatings to aluminum substrates.
Therefore, according to a general aspect, it is an object of the present invention to provide an expansive coating composition that meets one or more of the above-mentioned desires of the industry.

This and other purposes are expansive coating compositions, which
(A)
-(A1) Polyepoxy functional compounds and, if necessary,
A resin component comprising- (a2) a beta-hydroxyester of (meth) acrylic acid and / or a (meth) acrylate functional compound different from the-(a3) compound (a2).
(B) A cross-linking agent component containing at least one compound (b1) having a plurality of functional groups having reactivity with the epoxy group of the polyepoxy functional compound.
(C) An organosilane compound of the formula (I) or (ii) and an organosilane compound selected from a combination thereof in an amount of 5 to 20% by weight based on the total weight of the expandable coating composition.
( _YL- ) _n -SiX _m Ro (I),
(YL) _u -B- (K-SiX _v R _w ) _z (II)
During the ceremony
-N and m are integers of 1 to 3, o is an integer of 0 to 2, and so on.
n + m + o is 4,
-Y is an integer of 1 to 3, w is an integer of 0 to 2, and y + w is 3.
-U is an integer of at least 1, z is an integer of at least 2.
-B is a polyvalent organic group, and the valence of B is u + z.
-L is a divalent organic group, or Y is a bond when it is a vinyl group.
-K is a divalent organic group or bond,
-Y is a functional group having reactivity with the epoxy group of the component (a) and / or the (meth) acrylate group when present, or the functional group of the component (b).
-X is independently selected from chloro, alkoxy, acyloxy, and oxyimino for each appearance.
-R is an organosilane compound which is a hydrocarbyl group, and
(D) A compound that provides an expansion gas during thermal decomposition and
The compounds defined for (a)-(d) are different from each other, and the expansive coating composition is liquid at atmospheric pressure of 23 ° C. and is less than 5% by weight based on the total weight of the composition. Achieved by a swellable coating composition comprising water.

INDUSTRIAL APPLICABILITY The present invention further relates to a method for coating a substrate, which comprises applying the expandable coating composition according to the present invention to a substrate at least partially and, if necessary, curing the applied coating composition. Regarding.

According to a further aspect, the present invention is directed to a substrate coated by the method and an article comprising the substrate.
Still according to a further aspect, the present invention relates to the expansive coating composition according to the present invention.
-To provide fire protection for the battery or battery case when applied to any part of the battery or battery case, and / or to reduce or prevent thermal runaway of the battery or battery case, or-battery and article In between, used to provide fire protection for an article with a battery when applied to a portion of the article adjacent to the battery.
The battery is intended for use, which is preferably a lithium-ion battery.

Still according to further aspects, the invention is to apply the curable expandable coating composition as defined according to the invention to any portion of the battery to form a coating on it, and on top of it. A method for providing fire protection to a battery or reducing or preventing thermal runaway of a battery by curing the coating to obtain a crosslinked expansive coating is of interest.

Still according to a further aspect, the invention applies the curable expandable coating composition as defined in accordance with the invention to a portion of the article adjacent to the battery between the battery and the article, and further. The subject is a method for providing fire protection to an article comprising a battery by forming a coating on the surface and curing the coating to obtain a crosslinked expansive coating on it. In particular, the article may be a vehicle, comprising a lithium ion battery and a passenger cabin, and the crosslinked inflatable coating is positioned to protect the passenger cabin of the vehicle from battery fire.

FIG. 5 is a graph showing the heat transfer of heat through an exemplary expansive coating of the present invention over time. FIG. 5 is a graph showing the heat transfer of heat through an exemplary expansive coating of the present invention over time. FIG. 5 is a graph showing the heat transfer of heat through an exemplary expansive coating of the present invention over time. FIG. 6 is a graph showing the heat transfer over time through some exemplary expansive coatings of the present invention.

Except for the embodiments of any operation, or otherwise indicated, all numbers representing the amounts of raw materials, reaction conditions, etc. used herein and in the claims are referred to as "about" in all examples. It should be understood as being modified by the term. Therefore, unless shown to be in conflict, the numerical parameters described in the following specification and the appended claims are approximate values that may vary depending on the desired properties obtained by the present invention. At the very least, it does not attempt to limit the application of equality to the scope of the claims, and each numerical parameter shall take into account the significant number of digits reported and apply the usual rounding techniques. Should at least be interpreted by.

Although the numerical ranges and parameters that describe the broad range of the invention are approximations, the numerical values described in a particular example are reported as accurately as possible. However, every number essentially contains certain errors that are inevitably obtained from the standard deviations found in their respective test measurements.

It should also be understood that any numerical range described herein is intended to include all subranges contained therein. For example, the range "1-10" is between (including) the stated minimum value 1 and the stated maximum value 10, that is, equal to or greater than the minimum value equal to 1 and equal to 10. It is intended to include all subranges with or less maximum values.

As used herein and in the appended claims, the articles "a", "an", and "the" include multiple references unless expressly and explicitly limited to one reference. For example, "polymer" ("a" polymer), "curing agent" ("a" curing agent), "carbon source" ("a" carbon source), "foaming agent" ("a" forming agent), " "An" acid source "(" an "acid source)," reinforcing fiber "(" a "reinforced fiber)," inorganic additive "(" an "inorganic additive)," coating composition "(" a "coating composition), etc. Although reference is made to, one or more of any of these components can be used.

As used herein, the term "hydrocarbyl" refers to a group containing a carbon atom and a hydrogen atom.

The term "long-chain hydrocarbon substituent" herein refers to hydrocarbyl having at least 6 carbon atoms.

As used herein, in the claims and throughout the specification, the term "battery" refers to an individual battery cell as well as a battery pack comprising multiple battery cells.

According to a general aspect of the invention, the expansive coating composition is:
(A)
-(A1) Polyepoxy functional compounds and, if necessary,
A resin component comprising- (a2) a beta-hydroxyester of (meth) acrylic acid and / or a (meth) acrylate functional compound different from the-(a3) compound (a2).
(B) A cross-linking agent component containing at least one compound (b1) having a plurality of functional groups having reactivity with the epoxy group of the polyepoxy functional compound.
(C) An organosilane compound of the formula (I) or (ii) and an organosilane compound selected from a combination thereof in an amount of 5 to 20% by weight based on the total weight of the expandable coating composition.
( _YL- ) _n -SiX _m Ro (I),
(YL) _u -B- (K-SiX _v R _w ) _z (II)
During the ceremony
-N and m are integers of 1 to 3, o is an integer of 0 to 2, and so on.
n + m + o is 4,
-Y is an integer of 1 to 3, w is an integer of 0 to 2, and y + w is 3.
-U is an integer of at least 1, z is an integer of at least 2.
-B is a polyvalent organic group, and the valence of B is u + z.
-L is a divalent organic group, or Y is a bond when it is a vinyl group.
-K is a divalent organic group or bond,
—Y comprises a functional group that is reactive with the epoxy group of component (a) and / or the (meth) acrylate group, if present, or the functional group of component (b).
-X is independently selected from chloro, alkoxy, acyloxy, and oxyimino for each appearance.
-R is an organosilane compound which is a hydrocarbyl group, and
(D) A compound that provides an expansion gas during thermal decomposition and
The compounds defined for (a)-(d) are different from each other, and the expansive coating composition is liquid at atmospheric pressure of 23 ° C. and is less than 5% by weight based on the total weight of the composition. Contains water.

Resin component (a)
The polyepoxy functional compound (a1) is not particularly limited. This includes, but is not limited to, oligomers or polymer compounds with multiple epoxy functional groups, such as epoxy resins.

An epoxy resin suitable for the resin component (a1) contains at least one polyepoxy. Polyepoxides have at least two 1,2-epoxy groups. Epoxy equivalents of polyepoxys are typically in the range of 80-6000, typically 100-700. The epoxy compound may be saturated or unsaturated cyclic, aliphatic, alicyclic, aromatic, or heterocyclic. These may include substituents (s) such as halogens, hydroxys, and ethers.

Examples of polyepoxides are polyglycidyl of polyphenols such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), resorcinol, hydroquinone, benzenedimethol, fluoroglucol, bisphenol F, and catechol. Ether, or 1,2-cyclohexanediol, 1,4-cyclohexanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-bis (4-hydroxycyclohexyl) ethane, 2-methyl-1,1 -Bis (4-hydroxycyclohexyl) propane, 2,2-bis (4-hydroxy-3-tert-butylcyclohexyl) propane, 1,3-bis (hydroxymethyl) cyclohexane, and 1,2-bis (hydroxymethyl) It is a polyglycidyl ether of a polyol such as an alicyclic polyol such as cyclohexane. Examples of aliphatic polyols include, in particular, trihydroxymethylpentanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,2, 6-Hexanetriol, cyclohexanedimethanol, glycerol, trimethyllolpropane, hydrogenated bisphenol A, hydrogenated bisphenol F, or polyether glycols such as poly (oxytetramethylene) glycol, poly (oxyethylene) glycol, Examples include poly (oxypropylene) glycol and neopentanediol.

Certain suitable polyepoxyds have an epoxy equivalent of less than 300 g / equivalent. This example is from Hexion Inc. Includes EPON828 commercially available from.

Another group of suitable epoxy resins include epoxy compounds such as epichlorohydrin and aliphatics such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, or dimerized linoleic acid. Alternatively, a polyglycidyl ether of a polycarboxylic acid, which is formed by a reaction with an aromatic polycarboxylic acid, can be mentioned.

Other suitable epoxy resins that can be used in accordance with the present invention include epoxidized olefinic unsaturated alicyclic materials such as epoxy alicyclic ethers and esters, epoxy resins containing oxyalkylene groups, and epoxy novolak resins. These are prepared by reacting epihalohydrin with a condensation product of an aldehyde with a monovalent or polyvalent phenol such as an epoxyphenol novolak resin or an epoxy cresol novolak resin.

Further, according to the present invention, it may be advantageous to use a flexible polyepoxyd resin as the polyepoxy functional compound (a1) of the expandable coating composition of the present invention. These resins are generally linear materials, although small amounts of branching are allowed. Examples of suitable materials are epoxidized soybean oil, dimer acid-based materials such as EMPOL1010 resin commercially available from BASF SE (Ludwigshafen Technology), and products prepared from polyglycidyl ethers and acid-functional polybutadienes of bisphenol A. Examples include rubber-modified polypoxyde resins such as.

Other suitable examples of flexible polyepoxy for use in accordance with the present invention include flexible acid functional polyesters and epoxy functional adducts prepared from polyepoxy.

Acid-functional polyesters generally have an acid value of at least 10 mgKOH / g, generally from about 140 to about 350 mgKOH / g, and more preferably from about 180 to about 260 mgKOH / g, as determined by ASTM974-87.

For use herein, straight polyesters are more suitable than branched polyesters. The acid-functional polyester can be prepared by polyesterifying an organic polycarboxylic acid or an anhydride thereof with an organic polyol. Usually, polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids and diols.

Commonly used diols for the production of polyesters include alkylene glycols such as ethylene glycol, diethylene glycol and neopentyl glycol, and other diols such as hydride bisphenol A, cyclohexanediol, cyclohexanedimethanol, caprolactone diols, such as epsilon-caprolactone. And ethylene glycol reaction products, hydroxy-alkylated bisphenols, polyether glycols such as poly (oxytetramethylene) glycols, poly (oxyethylene) glycols, poly (oxypropylene) glycols and the like. Polyols are more suitable, but higher functional polyols can also be used. Examples include higher molecular weight polyols such as trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, isosorbide, tetramethylcyclobutanediol, and those produced by oxyalkylating lower molecular weight polyols. Can be mentioned.

The acid component of polyester comprises a monomeric dicarboxylic acid or anhydride having 2-36 carbon atoms per molecule. Among the useful acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid, tetra. There are bromophthalic acid, decanedioic acid, dodecanedioic acid, logonic acid, diphenolic acid, gallic acid, and deals alder adducts of various types of other dicarboxylic acids such as unsaturated _C18 fatty acids.

Polyesters may contain small amounts of monobasic acids such as benzoic acid, stearic acid, acetic acid, hydroxystearic acid, and oleic acid. In addition, higher-grade polycarboxylic acids such as trimellitic acid may be used. When an acid is mentioned above, it is understood that the anhydride of the acid forming the anhydride can be used in place of the acid. Also, lower alkyl esters of acids such as dimethyl glutarate and dimethyl terephthalate can be used.

According to the present invention, the polyester used to make the epoxy functional adduct is a polycarboxylic acid component containing a polycarboxylic acid or a mixture of acids having 7 to 16 carbon atoms, and a part of diethylene glycol. It can be prepared from a polyol component containing.

The polyepoxy used to prepare the flexible acid-functional polyester and the epoxy-functional adduct of the polyepoxy can be selected from those defined above for the polyepoxy-functional component according to the invention.

Another suitable polyepoxy functional compound is an epoxy functional acrylic resin. Such resins can be prepared by free radical addition polymerization of (meth) acrylic monomers in combination with vinyl monomers or other monomers containing at least one carbon-carbon double bond, if desired. Includes at least one epoxy functional compound with one carbon-carbon double bond.

Suitable epoxy functional ethylenically unsaturated monomers are glycidyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether, vinyl cyclohexene oxide, limonene oxide, 2-ethyl glycidyl acrylate, 2-ethyl glycidyl methacrylate, 2- (n-). Propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2- (n-butyl) glycidyl methacrylate, glycidyl methyl methacrylate, glycidyl acrylate, (3', 4'-epoxy Heptyl) -2-ethyl acrylate, (3', 4'-epoxy heptyl) -2-ethyl methacrylate, (6', 7'-epoxy heptyl) acrylate, (6', 7'-epoxy heptyl) methacrylate, allyl- 3,4-Epoxyheptyl ether, 6,7-Epoxyheptyl allyl ether, Vinyl-3,4-Epoxyheptyl ether, 3,4-Epoxyheptyl vinyl ether, 6,7-Epoxyheptyl vinyl ether, o-vinylbenzyl glycidyl ether, It can be selected from m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-vinylcyclohexene oxide, alpha-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and combinations thereof. Glycidyl (meth) acrylates are particularly suitable.

Additional monomers suitable for the preparation of epoxy functional acrylic resins
-Ethylene unsaturated nitrile compound,
-Vinyl aromatic monomer,
-Alkyl ester of ethylenically unsaturated acid,
-Hydroxyalkyl esters of ethylenically unsaturated acids,
-Amid of ethylenically unsaturated acids,
-Ethylene unsaturated acid,
-Ethylene unsaturated sulfonic acid monomer and / or ethylenically unsaturated phosphorus-containing acid monomer,
-Vinyl carboxylate,
-Conjugated diene,
-A monomer having at least two ethylenically unsaturated groups, and-a combination thereof can be selected.

Examples of ethylenically unsaturated nitrile monomers that can be used in the preparation of epoxy functional acrylic resins are polymerizable unsaturated aliphatic nitriles containing 2-4 carbon atoms in a linear or branched arrangement. Monomers are mentioned, which can be replaced by either an acetyl group or an additional nitrile group. Examples of such nitrile monomers include acrylonitrile, methacrylonitrile, alpha-cyanoethyl acrylonitrile, fumaronitrile, and combinations thereof, and acrylonitrile is particularly suitable.

Representatives of vinyl aromatic monomers include, for example, styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, and vinyltoluene. Suitably, the vinyl aromatic monomer is selected from styrene, alpha-methylstyrene, and combinations thereof.

Examples of the (meth) acrylic acid ester that can be used in the preparation of epoxy functional acrylic resins include acrylic or (meth) acrylic acid n-alkyl esters in which the alkyl group has 1 to 20 carbon atoms, iso-. Reaction products of alkyl esters or tert-alkyl esters, methacrylics with glycidyl esters of neoacids such as versatic acid, neodecanoic acid, or pivalic acid, and monomers of hydroxyalkyl (meth) acrylates and alkoxyalkyl (meth) acrylates. Can be mentioned.

In general, suitable alkyl esters of (meth) acrylic acid can be selected from C ₁ to C ₂₀ alkyl (meth) acrylates, preferably C ₁ to C ₁₀ -alkyl (meth) acrylates. Examples of such acrylate monomers include n-butyl acrylate, secondary butyl acrylate, methyl acrylate, ethyl acrylate, hexyl acrylate, tert-butyl acrylate, 2-ethyl-hexyl acrylate, isooctyl acrylate, and 4-methyl-2-pentyl. Examples thereof include acrylate, 2-methylbutyl acrylate, methylmethacrylate, butylmethacrylate, n-butylmethacrylate, isobutylmethacrylate, ethylmethacrylate, isopropylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate, and cetylmethacrylate. The ester of (meth) acrylic acid can be selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and combinations thereof. Especially appropriate.

Hydroxyalkyl (meth) acrylate monomers that can be used in the preparation of epoxy functional acrylic resins include ethylene oxide, propylene oxide, and hydroxyalkyl acrylate and methacrylate monomers based on higher alkylene oxides, or mixtures thereof. Can be mentioned. Examples are hydroxyethyl acrylates, hydroxypropyl acrylates, hydroxyethyl methacrylates, hydroxypropyl methacrylates, and hydroxybutyl acrylates. Suitably, the hydroxyalkyl (meth) acrylate monomer is selected from 2-hydroxyethyl (meth) acrylate.

Amides of ethylenically unsaturated acids that can be used in the preparation of epoxy functional acrylic resins include acrylamide, methacrylamide, and diacetone acrylamide. A particularly suitable amide monomer is (meth) acrylamide.
Vinyl ester monomers that can be used to prepare epoxy functional acrylic resins include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl 2-ethylhexanoate, vinyl stearate, and versatic acid. Vinyl ester can be mentioned. A particularly suitable vinyl ester is vinyl acetate.

Suitable ethylenically unsaturated carboxylic acid monomers for the preparation of epoxy functional acrylic resins include monocarboxylic acid and dicarboxylic acid monomers, and dicarboxylic acid monoesters. It is particularly appropriate to use ethylenically unsaturated aliphatic monocarboxylic acids or dicarboxylic acids or anhydrides containing 3-5 carbon atoms to carry out the present invention. Examples of monocarboxylic acid monomers include acrylic acid, methacrylic acid, and crotonic acid, and examples of dicarboxylic acid monomers include fumaric acid, itaconic acid, maleic acid, and maleic anhydride. Examples of other suitable ethylenically unsaturated acids are vinyl acetic acid, vinyl lactic acid, vinyl sulfonic acid, 2-methyl-2-propen-1-sulfonic acid, styrene sulfonic acid, acrylamide methyl propane sulfonic acid, and these. Salt is mentioned. Suitably, the ethylenically unsaturated carboxylic acid monomer is selected from (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and combinations thereof.

Suitable conjugated diene monomers for the preparation of epoxy functional acrylic resins include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-. Chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-octadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1, 3-Pentadiene, 3,4-dimethyl-1,3-hexadiene, 2,3-diethyl-1,3-butadiene, 4,5-diethyl-1,3-octadien, 3-butyl-1,3-octadien, 3,7-dimethyl-1,3,6-octatriene, 2-methyl-6-methylene-1,7-octadien, 7-methyl-3-methylene-1,6-octadien, 1,3,7-octa Triene, 2-ethyl-1,3-butadiene, 2-amyl-1,3-butadiene, 3,7-dimethyl-1,3,7-octatriene, 3,7-dimethyl-1,3,6-octa Triene, 3,7,11-trimethyl-1,3,6,10-dodecatetraene, 7,11-dimethyl-3-methylene-1,6,10-dodecatriene, 2,6-dimethyl-2,4 , 6-Octatriene, 2-phenyl-1,3-butadiene and 2-methyl-3-isopropyl-1,3-butadiene, and conjugated diene monomers selected from 1,3-cyclohexadiene. 1,3-butadiene, isoprene, and combinations thereof are particularly suitable conjugated diene.

It is also possible to use in the resin component (a1) a combination of two or more different polyepoxy functional compounds, such as three or more or four or more, which may be selected from those disclosed above.

Suitable polyepoxy functional compounds according to the invention are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, epoxyphenol novolak resin, epoxy cresol novolak resin, epoxy functional (poly) siloxane, epoxy. It can be selected from functional polysilfides, epoxy functional additives of acid-functional polyesters, and polyepoxys, eg, those described above.

The beta-hydroxyester (a2) of (meth) acrylic acid, which is optionally present in the resin component (a) of the expansive coating composition of the present invention, results from the reaction of the polyepoxide with the (meth) acrylic acid (. Meta) It may contain multiple beta-hydroxyesters of acrylic ester groups. Polyepoxys are with (meth) acrylic acid 1: 0.1 to 1: 1.2, more appropriately 1: 0.5 to 1: 1.2, more preferably 1: 1 to 1: 1.05. The reaction can be carried out at the epoxy-carboxylic acid equivalent ratio of.

Polyepoxides that can be used in the reaction product of polyepoxides with (meth) acrylic acid can be selected from the polyepoxides disclosed above with respect to component (a1) of the expansive coating composition of the present invention. Particularly suitable epoxides that can be used to make the beta-hydroxyester (component (a2)) of the (meth) acrylic acid of the expansive coating composition according to the invention are bisphenol A diglycidyl ethers, bisphenol F. Diglycidyl ether, epoxy phenyl novolak resin, epoxy cresol novolak resin, epoxy functional acrylic resin, epoxy functional polyester, or a combination thereof.

A particularly suitable beta-hydroxyester of (meth) acrylic acid is a reaction product of EPIKOTE 828 (a reaction product of bisphenol A with epichlorohydrin) and acrylic acid, commercially available from Allnex as EBECRYL3720). ..

In addition to or as an alternative to the beta-hydroxyester (a2) of (meth) acrylic acid, a (meth) acrylate functional compound (a3) different from the compound (a2) may be present in the resin component (a). .. Thereby, the viscosity of the expandable coating composition of the present invention can be appropriately adjusted. Therefore, the required component (a3) is considered to function as a reactive diluent in the expansive coating composition of the present invention. The required (meth) acrylate functional component (ii) of the expansive coating composition of the present invention is 1,4-butanediol, neopentyl glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol. Propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, para-xylene glycol, 1,4-cyclohexanediol, trimethylolethane, tri It can be selected from methylolpropane, pentaerythritol, poly (meth) acrylates of polyether glycols (eg, poly (oxytetramethylene) glycols, poly (oxyethylene) glycols, poly (oxypropylene) glycols), and combinations thereof.

We found that the addition of a (meth) acrylate functional compound (a3) different from the beta-hydroxyester (a2) and / or (a2) of (meth) acrylic acid resulted in a significant cure rate of the coating composition. Found to bring about an increase in.

Without wishing to be bound by theory, this increase in cure rate is due to the acrylic group (i) of the beta-hydroxyester of (meth) acrylic acid, or a (meth) acrylate functional compound different from (i). It is believed to be due to the Michael addition reaction between ii) and the polyamine and / or polythiol functional compound.

In the expansive coating composition of the present invention, the polyepoxy functional compound (a1) may be present in an amount of 20-95% by weight, preferably 40-95% by weight, and beta-hydroxy of (meth) acrylic acid. The ester (a2) can be present in an amount of 5-80% by weight, preferably 5-60% by weight, in which the beta-hydroxy ester of the polyepoxy functional compound (a1) and (meth) acrylic acid. (Single or plural) Based on the total weight of (a2).

Further, in the expansive coating composition of the present invention, the polyepoxy functional compound (a1) may be present in an amount of 25-95% by weight, preferably 40-95% by weight, and is a beta of (meth) acrylic acid. -The hydroxy ester (a2) may be present in an amount of 5 to 75% by weight, preferably 5 to 60% by weight, and the (meth) acrylate functional compound (a3) different from the compound (a2) is 0 to 0 to. It can be present in an amount of 50% by weight, preferably 5-30% by weight, based on the total weight of compounds (a1), (a2), and (a3).

In the expandable coating composition of the present invention, the amount of the resin component (a) is 15 to 38% by weight, 22 to 36% by weight, or 23 to 30% by weight based on the total solid content weight of the expandable coating composition. It may be 10 to 40% by weight, such as%. Alternatively, the amount of polymer in the coating composition of the present invention is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19% by weight to 30, 31, 32, 33, 34, 35. , 36, 37, 38, 39, 40% by weight. Any combination of endpoints in the above range can be used to define the amount of polymer in the expansive coating composition of the present invention.

Crosslinker component (b)
The cross-linking agent component (b) used in the curable expandable coating composition according to the present invention is at least one compound having a plurality of functional groups reactive with the epoxy group of the polyepoxy functional compound (a1). As long as it contains (b1), it is not particularly limited. Curing can be done either at ambient temperature or when heated, and curing at ambient temperature is particularly suitable for the expansive coating composition according to the invention.

Suitable compound (b1) is
-Polyamine functional compounds appropriately selected from aliphatic polyamines, aromatic polyamines, polys (amine-amides), and combinations thereof, or-appropriately from polysulfide thiols, polyether thiols, polyester thiols, pentaerythritol-based thiols. The polythiol functional compound of choice, or-may be selected from a combination of these.

The polyamine curing agent is selected from aliphatic polyamines, aromatic polyamines, polyamine amides, polyether amines, for example, those commercially available from Huntsman Cooperation (The Woodlands, Texas), polysiloxane amines, polysulfide amines, or combinations thereof. Can be done. Examples include diethylenetriamine, 3,3-amino-bis-propylamine, triethylenetetraamine, tetraethylenepentamine, m-xylene diamine, isophoronediamine, 1,3-bis (aminoethyl) cyclohexane, bis (4-). Aminocyclohexyl) methane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, and diaminodiphenylsulfone, including polyamines and BASF under the VERSAMID trademark. Reaction products with aliphatic fatty acids such as the series of materials sold by can be used, the latter being particularly suitable.

In addition, any of the above polyamine adducts can be used. The polyamine adduct is formed by reacting the polyamine with a suitable reactive compound such as an epoxy resin. This reaction reduces the content of free amines in the curing agent, making it more useful in low temperature and / or high humidity environments.

Hardeners include, but are not limited to, Jeffamine D-230, Jeffamine D-400, Jeffamine 600, Jeffamine 1000, Jeffamine 2005, and Jeffamine 2070, but are not limited to Huntsman Corp. Various polyether amines such as various Jeffamines available from can also be used.

Various polyamides can also be used as the curing agent. In general, polyamides contain dimer fatty acids and polyethyleneamines, as well as reaction products of small amounts of monomeric fatty acids. Dimer fatty acids are prepared by oligomerization of monomeric fatty acids. The polyethyleneamine may be any higher grade polyethyleneamine such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, etc., with the most commonly used being diethylenetriamine. Polyamides can be used as the curing agent to ensure that the coating has a good balance between corrosion resistance and waterproof properties. In addition, polyamide can allow the coating to have good flexibility, proper cure rate, and other favorable factors.

The polythiol compound can be selected from polysulfide thiols, polyether thiols, polyester thiols, pentaerythritol-based thiols, or combinations thereof. A particularly suitable polythiol compound is Thiolast (copyright) G4, which is commercially available from Akzo Nobel Fundamental Chemicals GmbH & Co KG (Greiz, Germany).

In the swellable coating composition of the present invention, the equivalent ratio of the combined functional groups such as the epoxy group and the (meth) acrylate group in the component (a) to the functional group in the compound (b1) is 2: 1 to 1. It may be 1: 2, preferably 1.05: 1.0 to 1: 2, and particularly preferably 1: 1.4 to 1: 2.

In the swellable coating composition of the present invention, the amount of compound (b1) is 15-20% by weight, 16-19% by weight, or 17-19% by weight based on the total solid content weight of the swellable coating composition. It is typically 10 to 30% by weight. Alternatively, the amount of compound (b1) in the coating composition of the invention is 10, 11, 12, 13, 14, or 15% by weight to 18, 19, 20, 21, 22, 23, 24, or It may be 25% by weight. Any combination of endpoints in the above range can be used to define the amount of various curing agents in the expansive coating composition of the present invention.

The swellable coating composition of the present invention may also contain a curing accelerator. The curing accelerator is a kind of material capable of accelerating the curing of the resin, lowering the curing temperature, and shortening the curing time. Typical curing accelerators include aliphatic amine accelerators such as triethanolamine and triethylenediamine; anhydrous accelerators such as BDMA and DBU; polyetheramine catalysts; tin accelerators such as dibutyltin dilaurate and stanas octoate. Be done. In one embodiment of the invention, the curing accelerator is ANCAMINE K54 commercially available from Air Products.

The appropriate amount of cure accelerator is 0.1-5% by weight, more preferably 1-3% by weight, based on the total solid content weight of the expansive coating composition.

The cross-linking agent component (b) of the swellable coating composition of the present invention is contained in the Si—X functionality of the organosilane compound (c) of the swellable coating composition of the present invention and, if necessary, in the presence of water. It may further contain compound (b2) capable of undergoing a condensation reaction. Suitable compound (b2) can be selected from silanes of formula (III) or (IV),
R _k SiX _l (III)
R _m X _3-m SiR'SiR _n X _3-n (IV)
In the formula, R'is defined as an alkyl group of 1 to 20 carbon atoms, more preferably 1 to 4 carbon atoms, and R and X are the organosilane compounds of the expansive coating composition according to the invention. (C) is defined for the organosilane compound (c), which is discussed below and comprises a particularly suitable embodiment of (c).
k is an integer of 0 to 2, l is an integer of 2 to 4, and the sum of k + l is 4.
m and n are integers of 0 to 2, and m + n is 3 or less.

Particularly suitable compounds (b2) can be selected from tetraalkoxysilanes, hydrocarbyltrialkoxysilanes, and dihydrocarbyldialkoxysilanes, and hydrocarbyl groups can be appropriately selected from C1 _{- C4} alkyl and phenyl, alkoxy groups. Can be appropriately selected from C ₁ to C ₄ alkoxy.

Compound (b2) is 0-5% by weight, more preferably 0.1-4% by weight, more preferably 0.5-4% by weight, based on the total solid weight of the expansive coating composition. More preferably, it may be present in an amount of 0.5 to 3% by weight. It is particularly suitable when compound (b2) is not present.

Organosilane compound (c):
The organosilane compound (c) useful in the expansive coating composition according to the present invention is defined above. Suitable organosilane compounds (c) present in the expansive coating composition of the present invention can be selected from the organosilane compounds of formula (I) or (II).
-L is selected from an alkylene group and a cycloalkylene group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and a bond where Y is a vinyl group and / or-. K is selected from an alkylene group and a cycloalkylene group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and a bond, and / or -Y is an epoxy-containing group, an amino group. , Polyamino group, amide group, thiol group, carboxylic acid group, hydroxy group, (meth) acrylicoxy group, and vinyl group, and / or -X preferably has 1 to 4 carbon atoms. It is selected from an alkoxy group, a chloro group, an acyloxy group, and an oxyimimino group, preferably selected from an alkoxy group having 1 to 4 carbon atoms, and / or -R is _a C1 to _C4 alkyl group. , And / or -B is a polyvalent alkyl group, and / or -n is 1, o is 0, m is 3, and / or -u is 1. Yes, z is 2.

Suitable organosilane compounds are vinyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3- (meth) acrylicoxypropyltrialkoxysilane, aminoalkyltrialkoxysilane, aminoalkyldialkylmonoalkoxysilane, bis- ( Aminoalkyl) Dialkoxysilanes, thiolalkyltrialkoxysilanes, thiolalkylalkyldialkoxysilanes, thiolalkyldialkylmonoalkoxysilanes, and combinations thereof can be selected. Other suitable organosilane compounds are compounds according to formula (II), z of 2, known to those of skill in the art as dipodalsilanes, which are also commercially available. Particularly suitable silane compound (c) is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-butylideneaminooxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycid. Xipropyltriethoxysilane, 3- (meth) acrylicoxypropyltrimethoxysilane, 3- (meth) acrylicoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl Dimethylmethoxysilane, bis- (3-aminopropyl) dimethoxysilane, thiolethyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) propyl] diethylenetriamine, β It can be selected from-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis [3- (trimethoxysilyl) propyl] amine.

The coating composition according to any of the above embodiments, wherein the amount of the organosilane compound (c) is 5-18% by weight, preferably 10-18% by weight, based on the total weight of the expandable coating composition. thing. Appropriate lower bounds for the range of amounts of organosilane compound (c) are at least 5, at least 5, 5, at least 6, at least 6.5, at least 7, at least 7. 5, at least 8, at least 8.5, at least 9,5, at least 10, at least 10.5, at least 11, at least 11.5, at least 12, at least 12.5, at least 13, at least 13.5, at least 14, It may be at least 14.5 and at least 15% by weight. Appropriate upper limits of the range of the amount of organosilane compound (c) are at most 20, at most 19, 5, at most 19, and at most 18. based on the total weight of the expansive coating composition. 5, at most 18, at most 17.5, at most 17, at most 16.5, at most 16, at most 15.5, at most 15, at most 14.5, At most 14, at most 13.5, at most 13, at most 12.5, at most 12, at most 11.5, at most 11, at most 10.5, at most 10.5 May be 10% by weight. Those skilled in the art will appreciate that any range defined herein by any one of the above lower limits and any one of the above upper limits is disclosed herein.

The expandable coating composition of the present invention further contains, as the component (d), a compound that provides an expansion gas during thermal decomposition.

The expansive gas serves to foam and inflate the refractory expandable composition when exposed to high temperature flames. The charcoal formed as a result of this expansion is a thick multicell material that serves to insulate and protect the underlying substrate. The source of the expanding gas that can be used in the expanding coating composition of the present invention is a nitrogen-containing material. Examples of suitable nitrogen-containing materials include melamine, phosphate salts, guanidine, methylated melamine, hexamethoxymethylmelamine, urea, dimethylurea, melaminepyrophosphate, dicyandiamide, guanylurea phosphate, and glycine. Be done. Appropriately, melamine is used. Other conventional sources of expanding gas, such as materials that liberate carbon dioxide, can also be used. Examples are alkaline earth metals such as calcium carbonate or magnesium carbonate. Compounds that release water vapor when decomposed during heating, such as calcium hydroxide, magnesium dihydric, or aluminum trihydroxide, can also be used. Other examples of such compounds are boric acid, as well as boric acid derivatives such as boric acid esters and metal borates.

The appropriate amount of component (d) in the expansive coating composition of the present invention may be in the range of 0.1 to 25% by weight, preferably 1 to 10% by weight, where the weight percent is the composition. Based on the total solid content weight of.

The expandable coating composition of the present invention comprises a phosphorus source, a boron source, a zinc source, an acid source, a metal oxide, for example, pre-hydrolyzed tetraethyl orthosilicate, aluminum oxide, titanium isopropoxide, carbon. Select from sources, inorganic fillers, mineral fibers such as CHOPVANTAGE from PPG, Coatforce or Roxul fibers from Lapinus, leology additives, organic solvents, pigments, foam stabilizers, and combinations thereof, as required. It may contain the additive (f).

Sources of phosphorus as needed include, for example, phosphoric acid, monoammonium phosphate and diammonium phosphate, tris- (2-chloroethyl) phosphate, phosphorus-containing amides such as phosphorylamide, and melamine pyrophosphate. It can be selected from a variety of materials. Appropriately, the source of phosphorus is ammonium polyphosphate represented by the formula (NH ₄ ) _{n + 2} P _n O _{3n + 1} , where n is an integer of at least 2 and, appropriately, n is. It is an integer of at least 50. The swellable coating composition of the present invention may contain an amount of phosphorus in the range of 0.05-30% by weight, preferably 0.5-10% by weight, based on the total solid content weight of the coating composition. .. Phosphorus is believed to function as a charcoal accelerator in the swelling composition.

The source of zinc as needed can be selected from a variety of materials. Zinc material is thought to contribute to the formation of small cell structures in carbon. The small cells of charcoal provide better insulation of the substrate and can better maintain the integrity of the charcoal and adhere to the substrate even in the absence of external reinforcing material. Therefore, cracking of the charcoal and breakage from the substrate are minimized, providing stronger protection against the underlying steel. Examples of suitable materials that are sources of zinc include zinc salts such as zinc oxide, zinc borate and zinc phosphate, zinc carbonate, and zinc metals can also be used. Appropriately, zinc borate is utilized. The swellable coating composition of the present invention may contain an amount of zinc in the range of 0.1-25% by weight, preferably 0.5-12% by weight, based on the total solid content weight of the composition.

Sources of boron are ammonium borate or zinc borate, borates such as boron oxide, sodium borate, potassium borate, and ammonium borate, borate esters such as butyl boric acid or phenylboric acid, and these. Can be selected from combinations. The swellable coating composition of the present invention may contain an amount of boron in the range of 0.1-10% by weight, preferably 1-6% by weight, where the weight percent is based on the total solid content weight of the composition. ..

The acid source can be selected from ammonium phosphate, ammonium polyphosphate, diamonium diphosphate, diamonium pentaborate, phosphate-producing materials, boric acid, metal or organic borates, and combinations thereof. If present, the total amount of acid source may be 5-30% by weight based on the total solid content weight of the coating composition.

The expandable coating composition of the present invention further comprises a carbon source. The carbon source is converted to charcoal when exposed to fire or heat, thereby forming a fire protection layer on the substrate. According to the present invention, the carbon source is, for example, an aromatic compound and / or a toll oil fatty acid (TOFA), and / or a polyhydroxy such as pentaerythritol, dipentaerythritol, glycerol, oligomer glycerol, xylitol, mannitol, sorbitol. It may be a compound and a polymer such as polyamide, polycarbonate, polyurethane, or a combination thereof. As a result, the inventors of the present invention are surprised to find that a carbon source containing an aromatic compound and / or a tall oil fatty acid is used as a carbon source in the expansive coating composition of the present invention. It has been found that the resulting swellable coatings not only have comparable or even better fire protection properties compared to similar types of swellable coatings, but can also retain these required properties after low temperatures. It will also be recognized that polymers can also be a carbon source.

In the swellable coating composition of the present invention, the amount of carbon source is maximum, such as 5-18% by weight, 11-17% by weight, or 12-16% by weight, based on the total weight of the swellable coating composition. It may be 18% by weight. Alternatively, the amount of carbon source in the coating composition of the present invention is 5,6,7,8,9,10,11,12,13% by weight to 15,16,17,18% by weight. You may. Any combination of endpoints in the above range can be used to define the amount of various carbon sources in the expansive coating composition of the present invention.

Phosphorus, zinc, boron, and expanding gas can each be provided by separate source materials, or, instead, a single material is the source of two or more of the additional components described above. Please understand what you get. For example, melamine pyrophosphate can provide a source of both phosphorus and swelling gas.

If necessary, the reinforcing filler (e) can be selected from a large number of conventionally used materials, including fiber reinforcing agents and plate-shaped reinforcing agents that are more suitable than other fillers. Examples of fiber reinforcements include glass fibers, ceramic fibers such as aluminum oxide / silicon oxide, and graphite fibers. Plate-like enhancers include hammermill glass flakes, mica, and wollastonite. Other suitable fillers include metal oxides, titanium oxides, clay, talc, silica, diatomaceous earth, lapinus® fibers, and various pigments. Reinforcement fillers are believed to help control the expansion of the fire protection composition before and during charcoal formation so that the resulting charcoal is hard and uniform.

One advantage of the present invention is that the expansive coating composition can be dyed without compromising the fire protection and mechanical properties of the cured expansive coating. In particular, a reinforced filler, such as a white reinforced filler, does not need to be present to provide a hard and uniform charcoal. Therefore, the amount of white pigment and / or filler selected from aluminum oxide, silicon oxide, mica, wollastonite, titanium oxide, clay, talc, and diatomaceous compounds in the expansive coating composition is the composition. Based on the total weight, it may be less than 2% by weight, preferably 0 to 0.1% by weight, and the amount of the colored pigment, especially the black pigment, is at least 0.5 based on the total weight of the composition. It may be% by weight, preferably 1 to 5% by weight.

The swellable coating composition of the present invention may also contain various conventional additives such as rheological additives, organic solvents, foam stabilizers, pigments, flame diffusion control agents and the like. These raw materials are as needed and can be added in various amounts. In particular, the swellable coating composition according to the invention is liquid at 23 ° C. and atmospheric pressure (ie, 1 bar) and is substantially non-aqueous, i.e., based on the total weight of the swellable coating composition. It contains less than 5% by weight, more preferably less than 3% by weight, more preferably less than 1% by weight, or even intentionally added water.

As mentioned above, the crosslinked expansive coating expands above the activation temperature to induce thermal decomposition of compound (c) and, if necessary, carbonize. Upon the action of heat and fire, the expanded foam begins to carbonize, and the resin material and additional carbon sources present as needed exhibit stability at high temperatures and prolong the thermal runaway of the battery or individual battery cells. Form a porous carbon network that provides insulation to prevent, or at least suppress, over time.

The expandable coating composition can be configured as a two-package system,
The component (a) is contained in the first package (A), and is contained in the first package (A).
The component (b) is contained in the second package (B).
Compound (c) is second when compound (c) is contained in the third package (C) or when Y— is a functional group reactive with the compound in component (a). The compound (c) is present in the first package (A) if it is present in the package (B) of the above, or if Y- is a functional group reactive with the compound in the component (b). death,
The compound (d), which provides the expanding gas during pyrolysis, and any of the additives (e) and (f), if present, may be in any combination, package (A), (B), or. Included in any of (C), or in any combination of these packages, or in one or more additional packages (D), the package immediately prior to application of the coating composition. Is mixed with.

The composition is solvent-free and is particularly suitable for spray application. If desired, thinning can be achieved with various conventional solvents such as xylene, methylene chloride, or 1,1,1-trichloroethane.

The swellable coating composition of the present invention can be applied to provide various dry coating thicknesses as needed. Suitable dry coating thicknesses may range from 10 to 20,000 microns, such as 50 to 5000 microns, 100 to 2000 microns, and so on.

In a method for coating a substrate, the expansive coating composition of the invention is applied, at least partially, to the substrate and then cured, if necessary. Suitable substrates may be selected from metal substrates appropriately selected from aluminum and steel substrates, or plastic substrates appropriately selected from polycarbonate.

In particular, the expansive coating composition of the present invention can be applied to structural elements of batteries, especially lithium ion batteries. The battery can include an outer wall element defining the housing and, if desired, an inner wall element, and the inflatable coating composition is present on and / or the outer and / or inner side surfaces of any of the outer wall elements. In some cases, it is applied at least partially to any side of the inner wall element. The outer wall element and / or the inner wall element may include a material selected from any of composites, steel, aluminum, and polycarbonate.

The battery, in particular the lithium-ion battery, may be a battery pack with multiple individual battery cells, and the crosslinked expansive coating may be in the expanded and optionally carbonized state of the individual battery cells. At least some of them are positioned to insulate each other. In addition, the expandable coating composition can be applied to the battery pack housing wall and internal split wall as described above.

An inflatable coating composition is applied to a portion of the article adjacent to the battery between the battery and the article to insulate the article from the battery in order to provide fire protection for the article comprising the battery and the user of the article. It is also within the scope of the present invention. In such cases, conventional batteries or batteries according to the present invention can be used. The article may be, for example, a mobile phone, tablet, or laptop computer.

Alternatively, the article may be a vehicle such as a hybrid or electric vehicle, a bus, or a truck. In such vehicles, it is common to position the battery, especially the lithium-ion battery, as a flat battery pack under the vehicle body, eg, the floor of the vehicle body, due to the weight of the battery. In such cases, the inflatable coating of the present invention may be applied to the floor portion of the vehicle adjacent to the battery between the battery and the vehicle body. This ensures that in the event of a thermal runaway or battery fire, the vehicle body, especially the passenger cabin, is protected by a bridged inflatable coating to prevent the fire from spreading to the passenger cabin and passengers in the event of such an event. The temperature rise in the passenger cabin is limited over a long period of time so that the passenger cabin has sufficient time to safely escape from the vehicle.

The present invention is defined by the following aspects.
1. 1. A swellable coating composition
(A)
-(A1) Polyepoxy functional compounds and, if necessary,
A beta-hydroxyester of-(a2) (meth) acrylic acid and / or a (meth) acrylate functional compound different from the-(a3) compound (a2).
Including resin components and
(B) A cross-linking agent component containing at least one compound (b1) having a plurality of functional groups having reactivity with the epoxy group of the polyepoxy functional compound.
(C) An organosilane compound of the formula (I) or (II) selected from 5 to 20% by weight based on the total weight of the expandable coating composition and a combination thereof.
( _YL- ) _n -SiX _m Ro (I),
(YL) _u -B- (K-SiX _v R _w ) _z (II)
During the ceremony
-N and m are integers of 1 to 3, o is an integer of 0 to 2, and so on.
n + m + o is 4,
-Y is an integer of 1 to 3, w is an integer of 0 to 2, and y + w is 3.
-U is an integer of at least 1, z is an integer of at least 2.
-B is a polyvalent organic group, and the valence of B is
u + z,
-L is a divalent organic group, or Y is a bond when it is a vinyl group.
-K is a divalent organic group or bond,
—Y comprises a functional group that is reactive with the epoxy group of component (a) and / or the (meth) acrylate group, if present, or the functional group of component (b).
-X is independently selected from chloro, alkoxy, acyloxy, and oxyimino for each appearance.
-R is an organosilane compound which is a hydrocarbyl group, and
(D) Containing a compound that provides an expansion gas during thermal decomposition.
The compounds defined for (a)-(d) are different from each other and the expansive coating composition is liquid at atmospheric pressure at 23 ° C. and contains less than 5% by weight of water based on the total weight of the composition. , Expandable coating composition.
2. 2. For the organosilane compound of formula (I) or (II)
-L is selected from the alkylene and cycloalkylene groups having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and the bond when Y is a vinyl group and / or-. K is selected from an alkylene group and a cycloalkylene group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and a bond, and / or -Y is an epoxy-containing group, an amino group. , Polyamino group, amide group, thiol group, carboxylic acid group, hydroxy group, (meth) acrylicoxy group, and vinyl group, and / or -X preferably has 1 to 4 carbon atoms. Selected from alkoxy groups, and / or -R is a C1 _{- C4} alkyl group, and / or -B is a polyvalent alkyl group, and / or -n is 1, o. Is 0, m is 3, and / or -u is 1, and z is 2.
The coating composition according to embodiment 1.
3. 3. Organosilane compounds are vinyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3- (meth) acrylicoxypropyltrialkoxysilane, aminoalkyltrialkoxysilane, aminoalkyldialkylmonoalkoxysilane, bis- (aminoalkyl). ) Dialkoxysilane, thiolalkyltrialkoxysilane, thiolalkylalkyldialkoxysilane, thiolalkyldialkylmonoalkoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, β- (3,4-epoxycyclohexyl) ethyl The coating composition according to aspect 2, which is selected from trimethoxysilane and a combination thereof.
4. The coating composition according to any one of the preceding embodiments, wherein the amount of the organosilane compound is 5-18% by weight, preferably 10-18% by weight, based on the total weight of the expandable coating composition.
5. The polyepoxy functional compound (a1) is bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, epoxyphenol novolak resin, epoxy cresol novolak resin, epoxy functional acrylic resin, epoxy functional polyester, or The coating composition according to any one of the preceding embodiments, comprising these combinations.
6. Beta-hydroxyester (a2) of (meth) acrylic acid is present, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, epoxyphenol novolak resin, epoxy cresol novolak resin, epoxy functional acrylic. Containing multiple beta-hydroxy (meth) acrylic ester groups resulting from the reaction of the polyepoxide selected from the resin, epoxy functional polyester, or a combination thereof with (meth) acrylic acid, preferably (meth) acrylic acid. The beta-hydroxyester (a2) of the above comprises the product of reaction of the polyepoxide with the (meth) acrylic acid at an epoxycarboxylic acid equivalent ratio of 1: 0.1 to 1: 1.015. The coating composition according to one.
7. The (meth) acrylate functional compound (a3) is present and contains 1,4-butanediol, neopentyl glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2,4-trimethyl. -1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, para-xylene glycol, 1,4-cyclohexanediol, trimethylolethane, trimethylolpropane, pentaerythritol, and combinations thereof. The coating composition according to any one of the preceding embodiments, which is selected from the poly (meth) acrylates of the above.
8. Ingredient (a) is
With 20-100% by weight, preferably 40-95% by weight of the polyepoxy functional compound (a1),
With 0-75% by weight, preferably 5-60% by weight of beta-hydroxyester (a2) of (meth) acrylic acid,
It contains 0 to 50% by weight, preferably 5 to 30% by weight, a (meth) acrylate functional compound (a3) different from compound (a2), and the weight percent is compound (a1), (a2). , And based on the total weight of (a3),
The coating composition according to any one of the preceding embodiments.
9. Ingredient (b) is
-Polyamine functional compounds appropriately selected from aliphatic polyamines, aromatic polyamines, polys (amine-amides), and combinations thereof, or-appropriately from polysulfide thiols, polyether thiols, polyester thiols, pentaerythritol-based thiols. The coating composition according to any one of the preceding embodiments, comprising a polythiol functional compound of choice, or a combination thereof.
10. The equivalent ratio of the combined epoxy group and (meth) acrylate group in (a) to the functional group in (b) is 2: 1 to 1: 2, preferably 1.3: 1.0 to 1. .0: 1.3, the coating composition according to any one of the preceding embodiments.
11. Contains pigments and / or fillers (e)
-The total amount of white pigment and / or filler selected from aluminum oxide, silicon oxide, mica, wollastonite, titanium oxide, clay, talc, and diatomaceous earth compounds is 2% by weight based on the total weight of the composition. Less than, preferably 0-0.1% by weight,
-The amount of colored pigments, especially black pigments, is at least 0.5% by weight, preferably 1-5% by weight, based on the total weight of the composition.
The coating composition according to any one of the preceding embodiments.
12. From phosphorus sources, boron sources, zinc sources, acid sources, carbon sources, rheological additives, organic solvents, pigments, foam stabilizers, adhesion promoters, corrosion inhibitors, UV stabilizers, and combinations thereof. The coating composition according to any one of the preceding embodiments, further comprising the selected additive (f).
13. It is a multi-package coating composition and
The component (a) is contained in the first package (A),
The component (b) is contained in the second package (B),
If compound (c) is contained in the third package (C) or Y- is a functional group reactive with the compound in component (a), compound (c) is second. The compound (c) is present in the first package (A) if it is present in the package (B) of the above, or if Y- is a functional group reactive with the compound in the component (b). death,
The compound (d) that provides the expansion gas during pyrolysis, and any of the additives (e) and (f), if present, in any combination, package (A), (B), or Included in any of (C), or in any combination of these packages, or in one or more additional packages (D), the package immediately prior to application of the coating composition. Mixed in,
The coating composition according to any one of the preceding embodiments.
14. Coating a substrate comprising applying the expansive coating composition according to any one of embodiments 1 to 13 to the substrate at least partially and, if necessary, curing the applied coating composition. How to.
15. 14. The method of aspect 14, wherein the substrate comprises a metal substrate, optionally selected from an aluminum substrate and a steel substrate, or a plastic substrate, preferably selected from polycarbonate.
16. Substrate coated by the method according to aspect 14 or 15.
17. An article comprising the substrate according to aspect 16.
18. The article according to aspect 17, which is a battery, preferably a lithium ion battery, or a battery case.
19. A battery, preferably a lithium ion battery, or a battery case, wherein the inflatable coating composition defined in any one of embodiments 1-13 is an article adjacent to the battery between the battery and the article. The article according to aspect 17, which is applied to a part of the product.
20. The article is a vehicle comprising a battery case with a lithium ion battery or a set of batteries, a passenger cabin, and an inflatable coating composition on the floor of the vehicle adjacent to the battery between the battery and the vehicle body. The article according to aspect 17, which is applied to at least a part of a portion.
21. -To provide fire protection for the battery or battery case when applied to any part of the battery or battery case, and / or to reduce or prevent thermal runaway of the battery or battery case, or-battery and article The use of the expansive coating composition according to any one of aspects 1-13 to provide fire protection for the article comprising the battery when applied to a portion of the article adjacent to the battery in between. hand,
The battery is properly a lithium-ion battery, used.
22. 21. The use according to aspect 21, wherein the article is a vehicle comprising a lithium ion battery and a passenger cabin, and a curable expandable coating composition is used to protect the passenger cabin of the vehicle from a battery fire.
23. The expansive coating composition according to any one of aspects 1 to 13 is applied to any portion of the battery to form a coating on it, thereby providing fire protection to the battery or heat of the battery. A method for reducing or preventing runaway, wherein the battery is appropriately a lithium ion battery.
24. The expansive coating composition according to any one of embodiments 1 to 13 is applied to a portion of the article adjacent to the battery between the battery and the article to form a coating on the battery. A method for providing fire protection for an article equipped with.
25. 24. The method of aspect 24, wherein the article is a vehicle comprising a lithium ion battery and a passenger cabin, and a crosslinked inflatable coating is positioned to protect the passenger cabin of the vehicle from battery fire.

The following examples are intended to illustrate the invention and are not intended to limit it.

Example 1
The following base components and curing agent components were mixed and completely mixed.

The mixture was sprayed onto an aluminum panel (5005H24 type) having a thickness of 0.8 mm and cured at 23 ° C. for a minimum of 7 days. The thickness of the dry coating of the cured coating was 150 μm.

On the back of the coated sample, a thermocouple was attached to the center point and the temperature was monitored through the sample. The center of the coated panel was then positioned at a distance of 4 cm from the propane torch (3.5 cm in diameter, propane) with the crosslinked expansive coating oriented towards the torch. The temperature of the flame was monitored through a second thermocouple placed near the base of the flame and found to remain stable at 900-1000 ° C. The temperature of the back surface of the coated substrate was measured over a long period of time. The results are shown in FIG.

Example 2
Example 1 was repeated, except that the following base formulation and curing agent formulation were used.

The results are shown in FIG.

Example 3
Example 1 was repeated, except that the following base formulation and curing agent formulation were used.

The results are shown in FIG.

Example 4:
Mixing ratio (weight): Base / curing agent = 45.7 / 54.3
Silane content (% by weight) in the total composition: 11.62% by weight

Example 5:
Mixing ratio (weight): Base / curing agent = 44.8 / 55.2
Silane content (% by weight) in the total composition: 9.11% by weight

Example 6:
Mixing ratio (weight): Base / curing agent = 44.1 / 55.9
Silane content (% by weight) in the total composition: 6.82% by weight

Example 7 (comparison):
Mixing ratio (weight): Base / curing agent = 43.2 / 56.8
Silane content (% by weight) in the set: 4.17% by weight

Example 8 (comparison):
Mixing ratio (weight): Base / Hardener = 42.5 / 57.5
Silane content (% by weight) in the total composition: 2.01% by weight

Example 9 (comparison):
Mixing ratio (weight): Base / curing agent = 42.1 / 57.9
Silane content (% by weight) in the set: 0.81% by weight

The expansive coating compositions of Examples 4-9 were applied to the aluminum panel and tested as described for Example 1. The results are shown in FIG.

Claims (25)

A swellable coating composition
(A)
-(A1) Polyepoxy functional compounds and, if necessary,
A resin component comprising- (a2) a beta-hydroxyester of (meth) acrylic acid and / or a (meth) acrylate functional compound different from the-(a3) compound (a2).
(B) A cross-linking agent component containing at least one compound (b1) having a plurality of functional groups having reactivity with the epoxy group of the polyepoxy functional compound.
(C) An organosilane compound of the formula (I) or (II) selected from 5 to 20% by weight based on the total weight of the expandable coating composition and a combination thereof.
( _YL- ) _n -SiX _m Ro (I),
(YL) _u -B- (K-SiX _v R _w ) _z (II)
During the ceremony
-N and m are integers of 1 to 3, o is an integer of 0 to 2, and so on.
n + m + o is 4,
-Y is an integer of 1 to 3, w is an integer of 0 to 2, and y + w is 3.
-U is an integer of at least 1, z is an integer of at least 2.
-B is a polyvalent organic group, and the valence of B is
u + z,
-L is a divalent organic group, or Y is a bond when it is a vinyl group.
-K is a divalent organic group or bond,
—Y comprises a functional group that is reactive with the epoxy group of component (a) and / or the (meth) acrylate group, if present, or the functional group of component (b).
-X is independently selected from chloro, alkoxy, acyloxy, and oxyimino for each appearance.
-R is an organosilane compound which is a hydrocarbyl group, and
(D) Containing a compound that provides an expansion gas during thermal decomposition.
The compounds defined in (a) to (d) are different from each other.
An swellable coating composition that is liquid at atmospheric pressure at 23 ° C. and contains less than 5% by weight of water based on the total weight of the composition. For the organosilane compound of the formula (I) or (II)
-L is selected from the alkylene and cycloalkylene groups having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and the bond when Y is a vinyl group and / or-. K is selected from an alkylene group and a cycloalkylene group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and a bond, and / or -Y is an epoxy-containing group, an amino group. , Polyamino group, amide group, thiol group, carboxylic acid group, hydroxy group, (meth) acrylicoxy group, and vinyl group, and / or -X preferably has 1 to 4 carbon atoms. Selected from alkoxy groups, and / or -R is a C1 _{- C4} alkyl group, and / or -B is a polyvalent alkyl group, and / or -n is 1, o. Is 0, m is 3, and / or -u is 1, and z is 2.
The coating composition according to claim 1. The organosilane compound is vinyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3- (meth) acrylicoxypropyltrialkoxysilane, aminoalkyltrialkoxysilane, aminoalkyldialkylmonoalkoxysilane, bis- (amino). Alkyl) Dialkoxysilane, Thiolalkyltrialkoxysilane, Thiolalkylalkyldialkoxysilane, Thiolalkyldialkylmonoalkoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine, β- (3,4-epoxycyclohexyl) The coating composition according to claim 2, which is selected from ethyltrimethoxysilane and a combination thereof. The preceding claim, wherein the amount of the organosilane compound is 5 to 18% by weight, more preferably 10 to 18% by weight, based on the total weight of the expansive coating composition. Coating composition. The polyepoxy functional compound (a1) is a bisphenol A diglycidyl ether, a bisphenol F diglycidyl ether, an epoxyphenol novolak resin, an epoxycresol novolak resin, an epoxy functional acrylic resin, an epoxy functional polyester, and the like. Or the coating composition according to any one of the preceding claims, which comprises a combination thereof. The beta-hydroxy ester (a2) of the (meth) acrylic acid is present, and bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, epoxyphenol novolak resin, epoxy cresol novolak resin, epoxy functionality. It contains a plurality of beta-hydroxy (meth) acrylic ester groups resulting from the reaction of a polyepoxide selected from acrylic resin, epoxy functional polyester, or a combination thereof with (meth) acrylic acid, as described above (meth). Preliminary claims comprising the product of the reaction of the polyepoxide with (meth) acrylic acid in the beta-hydroxyester (a2) of acrylic acid at an epoxycarboxylic acid equivalent ratio of 1: 0.1 to 1: 1.015. The coating composition according to any one of the items. The (meth) acrylate functional compound (a3) is present, and 1,4-butanediol, neopentyl glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2,4- Trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, para-xylene glycol, 1,4-cyclohexanediol, trimethylolethane, trimethylolpropane, pentaerythritol, and these. The coating composition according to any one of the preceding claims, selected from a combination of poly (meth) acrylates. Ingredient (a) is
With the polyepoxy functional compound (a1) of 20 to 100% by weight, preferably 40 to 95% by weight,
From 0 to 75% by weight, preferably 5 to 60% by weight of the beta-hydroxyester (a2) of the (meth) acrylic acid,
The (meth) acrylate functional compound (a3), which is different from the compound (a2), is contained in an amount of 0 to 50% by weight, preferably 5 to 30% by weight, and the weight percent is the compound (a1), ( The coating composition according to any one of the preceding claims, based on the total weights of a2) and (a3). The component (b) is
-Polyamine functional compounds appropriately selected from aliphatic polyamines, aromatic polyamines, polys (amine-amides), and combinations thereof, or-appropriately from polysulfide thiols, polyether thiols, polyester thiols, pentaerythritol-based thiols. The coating composition according to any one of the preceding claims, comprising the polythiol functional compound of choice, or a combination thereof. The equivalent ratio of the combined epoxy group and (meth) acrylate group in (a) to the functional group in (b) is 2: 1 to 1: 2, preferably 1.3: 1.0 to. The coating composition according to any one of the preceding claims, which is 1.0: 1.3. Further comprising a pigment and / or a filler (e)
-The total amount of white pigment and / or filler selected from aluminum oxide, silicon oxide, mica, wollastonite, titanium oxide, clay, talc, and diatomaceous earth compounds is 2 based on the total weight of the composition. Less than% by weight, preferably 0-0.1% by weight,
-The amount of the colored pigment, particularly the black pigment, is at least 0.5% by weight, preferably 1-5% by weight, based on said total weight of the composition.
The coating composition according to any one of the preceding claims. From phosphorus sources, boron sources, zinc sources, acid sources, carbon sources, rheological additives, organic solvents, pigments, foam stabilizers, adhesion promoters, corrosion inhibitors, UV stabilizers, and combinations thereof. The coating composition according to any one of the preceding claims, further comprising the selected additive (f). The coating composition according to any one of the preceding claims, which is a multi-package coating composition, wherein the coating composition is described herein.
The component (a) is contained in the first package (A),
The component (b) is contained in the second package (B),
The compound (c) is said when the compound (c) is contained in the third package (C) or Y-is a functional group reactive with the compound in the component (a). If Y- is a functional group that is present in the second package (B) or has reactivity with the compound in the component (b), the compound (c) is the first package (A). ) Exists in
The compound (d), which provides an expansion gas during thermal decomposition, and any of the additives (e) and (f), if present, may be in any combination of the packages (A), (B). , Or in any of (C), or in any combination of these packages, or in one or more additional packages (D), wherein said package is the coating composition. Mixed just before the application of
Coating composition. A substrate comprising applying the expandable coating composition according to any one of claims 1 to 13 to a substrate at least partially, and optionally curing the applied coating composition. How to coat. 14. The method of claim 14, wherein the substrate comprises a metal substrate, appropriately selected from an aluminum substrate and a steel substrate, or a plastic substrate, preferably selected from polycarbonate. A substrate coated by the method of claim 14 or 15. An article comprising the substrate according to claim 16. 17. The article of claim 17, which is a battery, preferably a lithium ion battery, or a battery case. A battery, preferably a lithium ion battery, or a battery case, wherein the expansive coating composition as defined in any one of claims 1 to 13 is applied to the battery between the battery and the article. The article according to claim 17, which is applied to a part of the adjacent articles. The article is a vehicle comprising a battery case with a lithium ion battery or a set of batteries, and a passenger cabin, wherein the inflatable coating composition is adjacent to the battery between the battery and the vehicle body. The article according to claim 17, which is applied to at least a part of the floor portion of the vehicle. -To provide fire protection for the battery or the battery case and / or to reduce or prevent thermal runaway of the battery or the battery case when applied to any part of the battery or battery case, or-battery The item according to any one of claims 1 to 13, for providing fire protection to the article comprising the battery when applied to a portion of the article adjacent to the battery between The use of expansive coating compositions,
The battery is preferably a lithium ion battery, used. 21. The article is a vehicle comprising a lithium ion battery and a passenger cabin, wherein the curable inflatable coating composition is used to protect the passenger cabin of the vehicle from battery fire. Use of. The expansive coating composition according to any one of claims 1 to 13 is applied to any portion of the battery to form a coating on the expansive coating composition to provide fire protection for the battery or to provide fire protection for the battery. A method for reducing or preventing thermal runaway, wherein the battery is preferably a lithium ion battery. The expandable coating composition according to any one of claims 1 to 13 is applied to a part of the article adjacent to the battery between the battery and the article to form a coating on the portion. By means of providing fire protection for the article comprising the battery. 24. The method of claim 24, wherein the article is a vehicle comprising a lithium ion battery and a passenger cabin, and a crosslinked inflatable coating is positioned to protect the passenger cabin of the vehicle from battery fire. ..

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